Glyoxal-amide reaction products



United States Patent 3,111,522 GLYDXAL-ARHDE REACTION PRODUCTS Sidney L.Vail, Clifford M. Moran, and Harry B. Moore,

New Orleans, La., assignors to the United States of America asrepresented by the Secretary of Agriculture No Drawing. Filed Feb. 2,1962, Ser. No. 170,848

5 Claims. (Cl. 260-268) (Granted under Title 35, US. Code (1952), see.266) A non-exclusive, irrevocable, royalty-free license in the inventionherein described throughout the world for all purposes of the UnitedStates Government, with the power to grant lSUbllCCHSBS for suchpurposes, is hereby granted to the Government of the United States ofAmerica.

This invention relates to the formation and use of compounds having thefollowing general structure:

wherein X= CR or -CR CR and where R is a member of the group consistingof H and an alkyl group of one to four carbon atoms. These compounds,which are similar in structure to the urea-glyoxal adducts, may be usedin resin applications, textile finishing, pharma ceutical, and alliedindustries, or as intermediates in these fields. Moreover, thesecompounds may also be used as glyoxal generators; that is, underconditions of heat and/or acid, glyoxal (and the starting bis-amide) canbe generated from the parent compounds.

The compounds of this invention are formed by the reaction of thebisarnide,

with glyoxal. Since one mole of the bisamide reacts with one mole ofglyoxal to form the desired compounds, it is preferable to react thestarting materials on a near equirnolar basis. In some cases an excessof the bisamide is useful to concentrate the solution and aids in theprecipitation of the desired compounds. The reaction has been found toproceed at low temperatures (about 25 C. has been found satisfactory toinitiate the reaction) and at varying pHs. Extreme acid or basicconditions should be avoided to exclude undesirable side reactions.

In general, it has been shown that N-methylol groups of amides, ureas,and similar compounds are reactive with a variety of materials.Difunctional compounds of this type are known to readily form usefulpolymers and serve as eifective cross-linking agents. In a recentpublication [American Dyestuff Reporter 50, 550 (1961)], it has beenshown that the N-methylol groups need not only be free NCH OH groups tobe reactive, but that I NCHOH groups, when part of a ring system, arealso quite reactive.

For example, such compounds of this invention are useful in thecrosslinking of cellulosic fabrics or fibers. Furthermore, the absenceof NH groups in the molecule decrease the possibilities of chlorineretention and the subsequent disadvantages of yellowing or scorch damageto the fabric. These and other advantages, such as an unusually highresistance to acid hydrolysis, will be evident in the examples given.

The following examples are given by way of illustration and are not tobe construed as limiting. Many variations or additions within theseprocedures can be made, as will be readily apparent to those skilled inthe art. In the examples, all parts and percentages are by weight unlessnoted otherwise. The fabrics were tested by standard 3,111,522 PatentedNov. 19, 1963 methods: Crease recovery angle, Monsanto method,

EXAMPLE 1 1,4-d1'formy1-2,3-dihydroxypiperazine,

OH OH was prepared in the following manner: 11.6 gramsethylenebisformamide were added to 19.3 grams of a 30% solution ofglyoxal which had been adjusted to a pH of 7. After solution of thebisamide, the pH was raised to 8-9 with aqueous sodium hydroxide. Theproduct formed rapidly resulting in a pasty mass. Recrystallization fromethanol produced a white product. The 1,4-diformyl-2,3-dihydroxypiperazine was found to contain 41.37% carbon, 5.79% hydrogenand 15.98% nitrogen. The molecular weight of the compound isolated wasfound to be 176. (Theory: 41.38% carbon, 5.79% hydrogen and 16.09%nitrogen, and molecular weight 174 for CgH N O EXAMPLE 21,3-diformyl-4,S-dihydroxyimidazoline,

was prepared in the following manner: to 9.8 grams of neutralized 30%glyoxal solution were added 7.7 grams of methylenebisformamide and 10grams of water. The pH was adjusted to 89, and the solids dissolved byshaking. After standing at room temperature for about four hours, thesolution was stored at 5l0 C. Colorless crystals of1,3-diformyl-4,S-dihydroxyimidazolidine were obtained by filtration. Thecompound contained 17.54% nitrogen. (Theory: 17.50% nitrogen for s a zi) On heating in ethanol the starting materials are recovered.

EXAMPLE 3 1,3-diacetyl-4,S-dihydroxyimidazolidine,

([lHa /CE2 (3H3 O=C-fil 1TTC=O m n-( 111 OH OH was prepared in a mannersimilar to Example 2 using methylenebisacetamide as the startingbisamide. The product, recrystallized from 50% ethanol-50% acetone,melted at 176-177 C. and contained 14.79% nitrogen. (Theory: 14.89%nitrogen for C H N O EXAMPLE 4l,4-d-iformyl-2,3-dihydroxy-5-methylpiperazine,

was prepared from 3.9 grams of 30% glyoxal and 2.6 grams ofpropylenebisformamide (prepared from propylenediamine and ethylformate). The alkalinity of the solution was adjusted as before; andafter remaining at room temperature for about four hours, the solutionwas stored at 12 C. A White crystalline product, which melted at 163-164C. with decomposition, was isolated by filtration and found to contain14.72% nitrogen. (Theory: 14.89% nitrogen for C H N O EXAMPLE 51,4-diformyl-2,3-dihydroxypiperazine prepared as described in Example 1was dissolved in water, and an acid substance or a substance producingacidity at elevated temperatures was added to serve as a catalyst. Atextile fabric, cotton in this case, was immersed in the solution, andthe excess liquid removed mechanically. The fabric was pinned to aframe, dried, and cured. All these steps can be conveniently carried outwith conventional textile finishing equipment. Table I more fullydescribes the conditions used for this particular experiment.

Table I Catalyst Drying Curing Agent Concentration Catalyst Concen-Condi- Oonditration tions tions Pyridine HC]-- 2% 60 G./ 160 C./ 7min.3min.

4 EXAMPLE 6 In addition to being employed as the sole agent in thetreating solution, the agent described in Example 1 but with 4%formaldehyde added to the pad bath, and the fabric treated in the samefashion as in Example 5, produced a fabric with an even greater creaserecovery angle. In this case the crease recovery angle was increasedsome 71% over the untreated fabric.

EXAMPLE 7 1,3-diacetyl-4,5-dihydroxyimidazolidine and1,4-diformyl-2,3-dihydroxypiperazine were added to a dilute solution of2,4-dinitrophenylhydrazine, which was acidified with HCl. After about anhour, a precipitate, identified as the hydrazone of glyoxal, began toappear. Glyoxal generation appeared complete after 24 hours.

We claim:

1. 1,4-diformyl-2,3-dihydroxypiperazine.

2, 1,3-diformyl-4,S-dihydnoxyimidazolidine.

3. 1,3-diacetyl-4,S-dihydroxyimidazolidine. 4.1,4-diformyl-2,3-dihydroxy-S-methylpiperazine. 5. A compound representedby the formula 0 X 0 ll RCN BIT-CR HCOH OH OH wherein X is a member ofthe group consisting of CR and C-R CR R is a member of the groupconsisting of H and an alkyl group containing from one to four carbonatoms.

References Cited in the file of this patent UNITED STATES PATENTS2,493,381 Balassa Jan. 3, 1950 2,764,573 Reibnitz et al Sept. 25, 19562,794,754 Schroeder June 4, 1957 2,927,924 Mills Mar. 8, 1960 2,937,177Bach et al May 17, 1960 2,958,624 Bimber Nov. 1, 1960

5. A COMPOUND REPRESENTED BY THE FORMULA